Miticidal compositions



United States Patent 3,102,117 0 MITICIDAL (JGMPOSITIUNS Gerard C. Riley, Churchville, and Edward A. Nolan, Philadelphia, Pa., assignors to Rohm & Haas Company, Philadelphia, Pa, a corporation of Delaware N0 Drawing. Filed May 12, 1961, Ser. No. 109,505 15 Claims. (til. 167-390) This invention concerns pesticidal compositions which contain 1,1-bis(halophenyl)-2,2,2-trichloroethanol dissolved in an alkyl oleate in which the alkyl group contains one to two carbon atoms.

Pesticides, such as insecticides and miticides, are commonly formulated as emulsion concentrates and wettable powders for spray purposes, as dusts, and as aerosols. In the control of mites on agricultural and horticultural crops, it is common to apply emulsion concentrates or wettable powders in aqueous sprays. A particularly effective miticide for use in such sprays is l,l-bis (p -chlorophenyl) -2,2,2-trichloroetlranol. It is usual practice to use this agent in conjunction with other types of pesticidal agents. For this purpose emulsion concentrates or wettable powders of these other agents are used in the same aqueous mixture as this miticide.

Often when this is done there is incompatibility. This incompatibility usually manifests itself in the formation of agglomerates or curds. This phenomenon is commonly known as greasing out. The curdy or clabber-like material often accumulates at the surface of the spray mixture or on the sides of the spray tank and it may clog screens. Since it is not readily redispersed into the spray liquid, it is rendered unavailable for spray purposes. It

is also conceivable that this type of incompatibility could occur on a leaf surface :as well as in a spray tank when at least two pesticides are applied to leaf surfaces.

There are other situations wherein the pesticidal formulations of the art are reduced in effectiveness as when climatic conditions, such as low temperature, prevent the pesticidal formulations from acting in their optimum manner.

In the cold, for example, the 1,1-bis(halophenyl)-2,2,2- trichloroethanols as heretofore applied tend to become somewhat horny and thus become less active against mites. Yet these same compounds have been found highly effective under warmer conditions. It is, therefore, desired to so formulate them as to increase their activity under a wide range of climatic conditions. Of course, such formulations should not only be compatible with other common pesticidal formulations so as. to permit their conjoint application, but also they must be relatively nonphytotoxic to the host plants.

The l,l-bis(halophenyl)-2,2,2-trichloroethanols are miticidal agents, the preparation of which is described in US. Patents No. 2,812,280 and 2,812,362. The product, 1,1-bis(chlorophenyl)-2,2,2 trichloroethanol is a wellknown commercial miticide and there are various pesticidal compositions which utilize it as an active miticide.

In accordance with the present invention, emulsion concentrates and wettable powder formulations containing a l,l-bis(halophenyl)-2,2,2-trichloroethanol as an active mirticidal agent have been evolved which show excellent compatibility when admixed in a spray tank with other formulated pesticides, which promise favorable miticidal effectiveness under adverse .climatic conditions, and which have acceptable phytotoxic properties.

The emulsion concentrates of this invention comprise 1,l-bis(halophenyl)-2,2,2-tnichloroethanol dissolved in an alkyl oleate with the incorporation of emulsifying agent.

. The ratio of the 1,1=bis(halophenyl)-2,2,2-trich1oroethanol to alkyl oleate may be varied from one part of such compound to four parts of the alkyl oleate to 1.25 parts to one part. Preferably, the ratios are from 1:2 to 1:1.

Emusifying agents are used in the concentration range of about 9 to about 20% by weight based on the emulsifialble concentrate and preferably 10% to 15%.

If desired, other pesticides may be incorporated. For example, dinitroallcylphenyl, especially the dinitro(2- methylheptyl)-phenyl, esters of crotonic, acrylic, methacrylic, 5,,8-dimethylacrylic, and 4 pentenoic acids which have been shown to have miticidal, insecticidal, and fungicidal properties may be advantageously added to these concentrates, and likewise such insecticidal agents as 1,1,1- trichloro-2,2bis (p-chlorophen-yl) ethane, 1, 1-dichloro-2,2- bis(p-chlorophenyl)ethane, or 1,1-dichloro-2,2-bis(ethy1- phenyl)-ethane, phosphatic pesticides such as 0,0-dimethyl S-(LZ-diCBIbdthOXYCt-hfl) dithicphosphate, and l-na-phthyl N-methylcarbamate. It is often desirable to blend 1,1-bis(halophenyl)-2,2,2-trichloroethanol with pesticidal agents which kill mite predators and which, when used alone, thus cause a build-up of the mite population. In general from 5 to 25% of pesticidal agents of the above type may be added to an emulsion concentrate. The percentage depends in part on the solubility of the particular pesticidal agent being incorporated.

The wettable powder formulations of this invention are made by mixing an inert, finely-divided, solid carrier with the emulsion concentrate. There may be used from 5% to 25% by weight of 1,l bishalophenyl)-2,2,2-trichl0roethanol in such compositions, this compound being dissolved in alkyl oleate together with emulsifiers. The amount of the emulsion concentrate added to the inert solid will vary with the capacity of each individual carrier or combination of carriers to hold the liquid and still maintain the product as a powder of loose texture.

The preferred 1,l bis(halophenyl)-2,2,2-trichloroethan- 01 used in this invention is 1,1-bis(p-chlorophenyl)-2,2,2- 'trichloroethanol. It may be used in a pure form or as a technical grade containing isomers having bis(orthochlorophenyl) groups and the p, o dichlorc-dip henyl groups as minor components. Also, the corresponding bromophenyl and fluorophenyl analogs may be used alone or admixed with 1,l-bis(chloropheny1) -2,2,2-trich1oroethanol.

As the solvent for the preparation of the emulsion concentrates there is used methyl oleate, ethyl oleate, or mixtures of these two. One purpose of the solvent is to act as a plasticizer for the l,l-bis(-halophenyl)-2,2,2-trichloroethanol and thus keep the active ingredient in a fluid condition at low temperatures. It is also desirable to have the emulsion concentrates flowable after prolonged storage at ambient temperatures in cold weather. 'For these reasons the oleic acid ester or mixture of esters used must have a low setting point; i.e., the temperature range wherein a solid forms. This point will vary with purity of the oleates and should be no more than 60 (about 16 C.). There may be used relatively pure alkyl oleates or commercially available technical products.

As emulsifying agents there may be used surface active ethylene oxide adducts of alkyl mercaptans, long-chained carboxylic acids, higher alcohols, and alkylphenols wherein the ethylene oxide content of the resulting product is about 15 to 100 ether units, preferably 20 to units. In general the alkyl mercaptans and higher alcohols should have 10 to 20 carbon atoms in their alkyl groups, while the acids should contain 12 to 24 carbon atoms in their carboxylic portion, which may be a straight or branched chain or a cycle, as in abietic acid. Typical of these are t-tetradecylthiopolyethoxyethanol, tall-oil-acid polyethoxyethanol, dodecyloxypolyethoxyethanol, and alkylphenoxypolyethoxyethanol, wherein the alkyl group or groups contain 8 to 12 carbon atoms and the main group occurs preferably in the para position but that position is immaterial. There may also be used ethylene oxide adducts -dodecylbenzenesulfonate.

pesticides.

"of'partia'l-ly esterified sorbitols and similar polyhydric alcohols, the esters being formed with such long-chained acids as oleic or lauric acids.

Also, there are used surface active, oil-soluble calcium and magnesium salts of alkylarenesulfonic aoids wherein the alkyl group or groups contain from 8 to 18 carbon atoms in admixtures with the above described ethylene 'oxide adducts. The preferred sulfonates are salts of alkylbenzenesulfonic acid, such as calcium p-t-dodecylbenzenesulfonate. There may also be used similar'alkyl 'naphthalenesulfonic acid salts, such as oalcium'octylnaphthalenesulfonates.

The ratio of weights of the ethylene oxide adduct to the sulfonate may vary from about 3 :1 to about 1:1.

' To prepare the wettable powders from the emulsion concentrates, a variety of finely dispersed solid carriers for the preparation of these wettable powders are the finely particled clays such as fullers earth and kaolins,

silica, diatomaceous earth, and alkaline earth silicates,

particularly those silicates which have been carbonated to'neutralize any basic impurities.

It is often desirable to incorporate dispersing agents I into the wettable powders. Typical of these are the salts of polymers formed from maleic anhydride and olefinically unsaturated hydrocarbons such as styrene, alkylstyrenes, or diisobutylene. When ammonia or some amines are used to form salts, some amide orimide formation also occurs. The amount of the added dispersit has good suspendibility in waters of varying hardness, and its application properties to foliage are entirely acceptable from its aqueous sprays.

In place of the above sodium salt used as a dispersant there may be used other common dispersing agents such as sodium or calcium lignosulfonates. These serve to provide good suspendibility, but it has been observed that compositions utilizing these sulfonates tend to deteriorate on extended storage. This improvement in suspendabili-ty in recently prepared mixtures is also observed when the dispersing agent is a salt of a condensed formaldehyde-naphthalene sulfonate such as sodium formaldehyde-naphthalene sulfonate as sold under the trade names of Daxad or Tamol.

ingagent is desirably 1% to 10% of the weight of the powderto which it is added.

Typical formulations and products of this invention are illustrated by the following examples. Parts are by weight unless otherwise designated.

'added 5' parts of p-diisobutylphenoxypolyethoxyethanol containing about 30 ether groups and 5 parts of calcium The mixture is stirred and warmed until homogeneous.

The resulting emulsion concentrate may be diluted with water to provide an efficient spray for protection against mites. It is compatible Wtih wettable powders containing fungicides such as wettable sulfur, ferbam, zineb, and

" maneb, with DDT, and with phosphatics.

(b) There are taken 50 parts of the above emulsion This powder is compatible with preparations of other Example 2 methylbenzenesulfonate. The product is useful and effecfive as an emulsion concentrate and can be diluted with water for spraying. It is compatible with the usual preparations of other pesticides.

(b) There are mixed 40 parts of the above emulsion concentrate, 50 parts of hydrated silica, and 10 parts of fullers earth. The mixture is then blended with five parts of 'the sodium salt formed from the copolymer from equal moles of maleic anhydride and diisobutylene. The resulting wettable powder is readily dispersed in water,

Example 3 (a) There are mixed 20 pants of technical 1,1-bis(cl1'lorophenyl)-2,2,2-trichloroethanol, 65' parts of methyl oleate (set point about 0 C.), and 15 parts of anemulsifier from 10 parts of long-chained fatty acid-ethylene oxide adduct, having'about ether groups perjmolecule and 5 parts of calcium tetradecylbenzenesulfonate. The resulting emulsion concentrate is stable on storage and is readily dispersed in even hard water to give effective aqueous sprays.

(b) There are mixed 50 parts of the above emulsion concentrate and 50 parts of finely divided sodium silicoaluminate (Zeolex 23) to form a useful wettable powder. The initial suspendibility is very good for this product, but storage characteristics are improved lay lblending therewith 3 to 10% of the ammonium salt of the copolymer from maleic anhydride, diisobutylene, and styrene.

The above formulation, repeatedwith substitution of an equal weight of ethyl oleate for the methyl oleate, provides another eflicient emulsion concentrate which, when blended with finely divided carriers, gives useful wettable powders. There may likewise be'used mixtures of methyl and ethyl oleates with like outcomes.

The emulsion concentrates of this invention can be readily formulated so as to he acceptably low in phytotoxicity on plants, even on flush citrus growth. Thisis also true of properly formulated wettable powders. 1 Since the alkyl oleates :are very high boiling and havehigh flash points, they can be used in grinding-machinery without hazard. Because of thelow volatility of the alkyl oleates the active agents remain in a fluid and active state. Most important of all, however, is the unusual degree .ofcom- I patibility of compositions of this invention with man common formulations of other pesticides.

We claim: 1. A miticid-al composition comprising asian active miticidal agent a 1,1-bis(halophenyl)-2,2,2 trichloroethanol dissolved in an alkyl oleate'in which the alkyl group contains one to two carbon atoms together with emulsify- 'ing agents consisting of a surface active ethyleneoxide adduct having 15 to 100 ether units and a-surfaceactive oil-soluble alkylarenesulfon-ate, the ratio of the ethylene oxide adduct to the alkylarenesulfonate varying' from about 3:1 to about 1:1 by weight.

2. A miticidal composition comprising'asian active miticidal agent 1,1-bis(chlorophenyl)-2,2,2-triohloroethanol and emulsifying agents dissolved in an alkyl oleate in which the alkyl group contains one to two carbon atoms, the ratio of said 1,1- bis(chlorophenyl)-2,2,2-trichloroethanol to said alkyl oleate 'being from 1:4 to 1.25 :1 and the emulsifying agents consisting of a surface active ethylene oxide adduct having 15 to 100 ether units and a surface active oil-soluble alkylarenesulfonate, theratio of the ethylene oxide adduct to the ialkylarenesulfonate I varying from about 3:1 to about 1:1 by weight.

3. A miticidal composition in the form of a wettable powder comprising a finely divided inert solidcarrying a solution of 1,1-bis(-chlorophenyl)-2,2,2-trichloroethanol and emulsifying agents in an alkyl oleate in which the arenas/o alkyl group contains one to two carbon atoms, the ratio of said 1,1-bis (chlorophenyl)-2,2,2-trichloroethanol to said alkyl oleate being from 1 :4 to 1.25:1 and the emulsifying agents consisting of a surface active ethylene oxide adduct having to 100 ether units and a surface active oil-soluble alkylarenesu-lfonate, the ratio of the ethylene oxide adduct to the alkylarenesulfonate varying from about 3:1 to about 1:1 by Weight.

4. A rniticidal composition comprising a solution of 1,1-bis(chlorophenyl)-2,2,2-trichloroethancl and emulsifying agents in at least one alkyl oleate in which the alkyl group contains one to two carbon atoms, the ratio of said l,l-bis(chlorophenyl)-2,2,2-trichloroethanol to said alkyl oleate being from 1:4 to 1.25:1 and the emulsifying agents consisting of a surface active ethylene oxide adduct having 15 to 100 ether units and a surf-ace active, oil-soluble alkylbenzenesulfonate wherein the alkyl group contains from 8 to 18 carbon atoms, the ratio of the ethylene oxide adduct to the alkylbenzenesulfonate varying from about 3:1 to about 1:1 by weight, the said emulsifying agents providing about 9% to of the weight of the solution.

5. A miticid al composition in the form of a wettable powder comprising a finely divided inert solid carrying a solution of 1,1-bis(chlorophenyl)-2,2,2-trichloroethanol and emulsifying agents in an alkyl oleate in which the a-llryl group contains one to two carbon atoms, the ratio of said 1,1-bis(chlorophenyl)-2,2,2-trichloroethanol to calcium alkylbenzenesu-lfonate is calcium dodecylbenzenesaid alkyl oleate being from 1:4 to 1.25 :1 land the emulsifying agents consisting of a surface active ethylene oxide adduct having 15 to 100 ether units and a surface active, oil-soluble ialkylbenzenesulfonate wherein the alkyl substituent contains from 8 to 18 carbon atoms, the ratio of the ethylene oxide adduct to the alkylbenzene sulfonate varying from about 3:1 to about 1:1 by Weight, the said emulsifying agents providing about 9% to 20% of the weight of the solution, and the percentage of the said 1,1-bis(chlorophenyl)-2,2,2-t1ich1oroethano=l being from 5% to 25% of the Weight of the composition.

6. A composition according to claim 5 in which there is added to the Wettable powder 1% to 10% by weight of a dispersing agent.

7. A composition according to claim 6 in which the dispersing agent is a salt of a polymer of maleic anhydride and =diisobutylene. i

8. A miticidal composition in the form of a Wettable powder comprising a finely divided hydrated silica carrying a solution of 1,1- bis(chlorophenyl)-2,2,2-trichloroethanol and emulsifying agents in methyl oleate, the ratio of said 1,1-bis-(ch1orophenyl)-2,2,2-trichloroethanol to said methyl oleate being from 1:4 to 1.25:1 and the emulsifying agents consisting of an alkylphenoxypolyethoxyethanol having 20 to 70 ether units and containing 8 to 12 carbon atoms in its alkyl substituent and a surface active, oil-soluble calcium alkylbenzenesulfonate wherein the alkyl substituent contains from 8 to 18 carbon atoms, the ratio of the alkylphenox'ypolyethoxyethanol to the calcium alkyl'benzenesulfonate being about 3:1 to

about 1:1 by weight, the said emulsifying agents providing about 9% to 20% of the Weight of the solution, and the percentage of the said 1,1-bis(chlorophenyl)-2,2,2-

sulfonate.

11. A miticidal composition comprising a solution of 1, 'l-bis (chlorophenyl -2,2,2-t-richloroethanol and emulsifying agents in methyl oleate, the ratio of said 1,1-bis- (ch lorophenyl)-2,2,2-trichloroethanol to methyl oleate being from 1:2 to 1:1 and the emulsifying agents consisting of an alkylphenoxypo lyethoxyethanol having 20 to other units and containing 8 to 12 carbon atoms in its alltyl substituent and a surface active, oil-soluble calcium alkylbenzenesulfonate wherein the alkyl substituent contains from 8 to 18 carbon atoms, the ratio of the ialkylphenoxypolyethoxyethanol to the calcium aikylbenzenesulfonate being about 3:1 to about 1:1 byweight, the said emulsifying agent providing about 9% to 20% of the weight of the solution.

12. A composition according to claim 11 in which the a1kylphenoxypolyethoxyethanol is diisobutylphenoxypolyethoxyethanol.

13. A composition according to claim 11 in which the calcium alkylbenzenesulfonate is calcium dodecylbenzenesu'lfonate.

14. A miticid al composition comprising :a solution of about 50% by weight of 1,l-bis(chlorophenyl)-2,2,2-trichloroethanol and 10% by weight of emulsifying agents in methyloleate, the emulsifying agents consisting of pdiisobutylphenoxypolyethoxyethano1 containing about 30 ether groups and calcium dodecylbenzenesulfonate in about equal weights.

15. A miticidal composition comprising about 50% by weight of a finely divided hydrated silica carrying about an equal weight of a solution of about 50 parts by weight of '1,l-bis(chlorophenyl)-2,2,24trichloroethano1 and 10 parts by weight of emulsifying agents dissolved in 40 parts by weight of methyl oleate, the emulsifying agents consisting of p-diisobutylphenoxypolyethoxyethanol containing about 30 ether groups and calcium dodecylbenzenesulfonate in about equal weights.

References Cited in the file of this patent UNITED STATES PATENTS? OTHER REFERENCES Mellan: Industrial Solvents, 2nd Ed., 19.50, published by Reinhold Publishing Corp, 330 West Forty-Second St, New York, New York, pages 166 (particularly page 16 2). 

1. A MITICIDAL COMPOSITION COMPRISING AS AN ACTIVE MITICICAL AGENT A 1,1-BIS(HALOPHENYL)-2,2,2-TRICHLOROERTHAND DISSOLVED IN AN ALKYL OLEATE IN WHICH THE ALKYL GROUP CONTAINS ONE TO TWO CARBON ATOMS TOGETHER WITH EMULSIFYING AGENTS CONSISTING OF A SURFACE ACTIVE ETHYLENE OXIDE ADDUCT HAVING 15 TO 100 ETHER UNITS AND A SURFACE ACTIVE OIL SOLUBLE ALKYLARENSULFONATE, THE RATIO OF THE ETHYLENE OXIDE ADDUCT TO THE ALKYARENESULFONATE VARYING FROM ABOUT 3:1 TO ABOUT 1:1 BY WEIGHT. 